Tertiary amine nitrogen-containing hydroxy-terminated polyether-based urethane compositions



United States Patent 3,105,963 TERTIARY AMlNE NITROGEN-CQNTAINWG HY-DROXY TERMINATE!) POLYETHER BASED URETHANE COMPOSITIONS Adolfas Damusis,Detroit, Mich, assignor to Wyandotte Chemicals Corporation, Wyandotte,Mich, a corporation of Michigan No Drawing. Filed Mar. 26, 1959, Ser.No. 802,017 12 Claims. (Cl. 260--77.5)

The present invention relates to novel branched tertiary aminenitrogen-containing hydroxy-terminated polyetherbased urethanecompositions which are useful as hydroxyterminated urethane componentsfor two-component polyurethane coatings or corresponding one packagesystems which employ as the other, or diisocyanate ingredient, a blockedisocyanate, and which are also of special utility as bodying agents forurethane coatings, particularly when it is not desired to employthermoplastic resins for such purpose.

It is an object of the present invention to provide novel bodying agentsfor urethane coatings. It is a further object to provide novel andvaluable branched tertiary amine nitrogen-containing hydroxy-terminatedurethane components for polyurethane coatings systems. A further objectis the provision of such compositions which are polyether-basedurethanes. Another object is the provision of such urethane compositionswhich lend advantageous properties to polyurethane coatings in whichthey are employed as the hydroxy-terminated component or ingredient.Still another object of the invention is the provision of a process forthe production of such urethane compositions by the reaction of onemolar proportion of a selected arylene diisocyanate with about two molarproportions of a selected tertiary amine nitrogen-containing polyetherpolyol, and the products thereby produced. Other objects of theinvention will become apparent hereinafter.

The foregoing and additional objects are accomplished by the provisionof branched urethane compositions of the following idealized formula:

0 Q-iiNH wherein R is selected from hydrogen and methyl, wherein y is anumber from zero to one, inclusive, and wherein Q is the same in bothoccurrences and is the radical of a branched tertiary aminenitrogen-containing polyether polyol (b), which is a propylene oxideaddition product of a tertiary amine nitrogen-containingpolyolcontaining at least three and not more than four hydroxy groups permolecule, said urethane composition being prepared by the reaction ofabout one molar proportion of arylene di-isocyanate (a) selected fromthe group consisting of phenylene diisocyanate, tolylene diisocyanate,and diphenylmethane-4,4'-diisocyanate, with about two molar proportionsof the selected branched tertiary amine nitrogen-containing polyetherpolyol (b).

Presence of the tertiary amine nitrogen in these urethane compositionsis very significant. It acts as a built-in catalyst, speeds up curing ofpolyurethane coatings embodying these hydroxy-terminated urethanes asone component or ingredient, and affects favorably the properties ofpolyurethane coatings formed therefrom by reaction with anisocyanate-tenninated component or ingredient. Properties favorablyaifected are surface hardness, film toughness, solvent resistance, andabrasion resistance.

The branched tertiary amine nitrogen-containing hydroxy-terminatedurethane compositions of the present invention have certain advantagesover ordinary hydroxylbearing materials such as polyesters and regularpolyols. Polyurethane coatings prepared therefrom by reaction with anisocyanate-tertrninated component dryto touch upon evaporation ofsolvent, and have considerably less sagging tendency than polyurethanecoating formulations incorporating regular polyols. When the branchedtertiary amine nitrogen-containing hydroxy-terminated urethanecompositions of the present invention are reacted with anisocyanate-terminated component, the resulting polyurethane surfacecoatings are characterized by properties which are superior to thoseobtained from the same isocyanate component and previously knownpolyhydroxy components. The same is true when they are employed as oneingredient of a one package surface coating cornposition together with ablocked diisocyanate as the other ingredient (for example, in bakingenamels or Wire coatings).

The branched tertiary amine nitrogen-containing hyroxy-terminatedurethane compositions of the present invention are prepared by reactingabout one molar proportion of an appropriate arylene diisocyanate (a),selected from phenylene diisocyanate, 2,4-tolylene diisocyanate,2,6-tolylene diisocyanate, including mixtures of 2,4 and 2,6-tolylenediisocyanates, and diphenylmethane- 4,4 diisocyanate, with about twomolar propontions of the selected tertiary amine nitrogen-containingbranched polyether polyol (b) to produce a hydroxy-terminated urethanecomposition in which the terminal hydroxy groups are furnished by thetertiary amine nitrogen-conv taining polyether polyol molecule.

The branched polyether polyol (b) used in the reaction is a propyleneoxide addition product of a tertiary amine nitrogen-containing polyol,and includes compounds oncompassed by the formula:

wherein Z is an alkylene radical containing from two through six carbonatoms, and wherein n is a number from one to three, inclusive,preferably not more than an average of two, and wherein x is a numberfrom zero to one, inclusive, which include, for example, the additionproducts of one mol of N,N,N',N-tetrakis(2-hydroxypropyl)ethylenediamine with four to 12 mols of propylene oxide, addition product of onemol of N,N,N',N'-tetra- =kis(2-hydroxypropyl)ethylene diamine with fourto 12 mols of propylene oxide and then with one mol of ethylene oxide,the corresponding higher alkylene diamines, such as the addition productof N,N,N,N'-tetrakis(2- hydroxypropyl) propylene diamine with from fourto 12 mols of propylene oxide and the mono ethylene oxide furtheraddition products thereof, the corresponding tetramethylene andhexamethylene diamines, and theN,N,N,N'-tetrakis(Z-hydroxypropyl)tetramethylene and hexamethylenediamine tetra through dodeca propylene oxide addition products thereofand such adducts further reacted with one mol of ethylene oxide, and thelike. Addition of one mol of ethylene oxide provides a primary hydroxylgroup of relatively high reactivity for definite direction andprecedence of reaction with NCO groups in preparing the OH-terminatedurethane.

Also included within the scope of the polyol (b) are compoundsencompassed by the formula:

1 C H:- O (0 5100) 11H wherein n is a number from one to three,inclusive, preferably not more than an average of two, and wherein x isa number from zero to one, inclusive, which include, for example, thetriisopropanolamine addition products with from three to nine mols ofpropylene oxide, and triisopropanolamine addition products with three tonine mols of propylene oxide and then with one mol of ethylene oxide,and the like.

In practice, the molecular weights of the branched tertiary aminenitrogen-containing hydroxy-terminated urethane compositions of theinvention, prepared in the given manner, have been found to be veryclose to the molecular weight of a composition having an idealizedstructure, since very little polymerization occurs using predeterminedmolar proportions under moderate reaction conditions, viz., exclusion ofmoisture and initial reaction temperature not above about 60 C. Also, inpractice, a tertiary amine nitrogen-containing polyol having no morethan about two propylene oxide units added per individual chain ofstarting polyol is usually preferred, and of the tertiary aminenitrogen-containing polyols, N,N,N',N-tetrakis(2-hydroxypropyl)ethylenediamine de rivatives are preferred. As for the isocyanate employed,tolylene diisocyanate, usually a mixture of about 80%/20% of the 2,4 and2,6-isomers, is preferred for reasons of economy. Other variations inthe starting materials to procure variations in the substituents of thebranched tertiary amine nitrogen-containing hydroxyterminated urethanecompositions may be usefully made to obtain polyurethane surfacecoatings of varying types and characteristics upon reaction with aselected polyisocyanate component. For example, lengthening of thepolyoxypropylene chains shown in the above formulae results in apolyurethane coating having a longer pot life, greater flexibility, andlower solvent resistance, while shortening of these polyoxypropylenechains has just the opposite eflFect. Flexibility of such coatings can,for example, be readily adjusted by changing the length of thepolyoxypropylene branches of the tertiary amine nitrogencontainingpolyol (b), if desired. The preferred equivalent weight of the tertiaryaminenitrogen-containing hydroxy-terminated urethanes of the presentinvention is between about 200 and 400.

The following examples are given to illustrate the present invention butare not to be construed as limiting.

GENERAL PROCEDURE Hydroxy-terminated urethanes, such as OH-INA ofExample 1, are prepared by reacting together about one mol of theselected arylene diisocyanate and about two mols of a tertiary aminenitrogen-containing polyether triol or tetraol in order to form ahydroxy-ter-minated urethane with free OH groups on both ends of themolecule. The addition of two tertiary amine nitrogen-containingpolyether triol molecules to the starting arylene diisocyanate makes theNCO/OH ratio 1/3.0, while two tetraol molecules makes the ratio 1/4.Dilution of the OH-termin-ated urethane, if desired, may be with anysuitable non-reactive surface coating solvent, or the reaction may beconducted in the presence of such a solvent. Many such solvents suitablein general for urethane coatings and components thereof are known in theart, for example, 2-ethoxyethyl acetate, 2-methoxyethyl acetate,2-butoxyethyl acetate, toluene, xylene, ethyl acetate, butyl acetate,amyl acetate, other similar esters, ketones, nitroaliphatic solvents,dioxane, and the like. In most instances no solvent is required duringthe reaction.

Tertiary amine nitrogen-containing polyether polyols used in thereaction are preferably stripped of water by azeotropic distillationwith toluene. In this manner, the amount of water can be decreased from0.08-0.15 to 0.2% or even less. A clean, dry, three-necked live-literflask was used as a reaction vessel, and a nitrogen blanket wasmaintained over the reactants.

Pr0cedure.--2736 parts of the polyoxypropylene derivative oftriisopropanolamine P-450T, 406 parts of Z-ethoxylethyl acetate and 406parts xylene are charged into a 5-liter reaction flask land are stirredgently. Tolyl-| ene diisocyanate is added gradually in portions. Thetemperature of the strongly exothermic reaction is kept below 60 C.Atiter the exothermic reaction stops, the contents of the reaction flaskare heated at 70 C. for 3 hours. Thereafter, the contents are cooled andbottled.

Properties of OH-INA:

NCO/0H 1/ 3 Avenage molecular weight 1080 Average equivalent weight 270Hydroxyl number 208 Percent hydroxyl 6.3 Properties of OH-INA solution:

Nonvolatile, percent Weight per gallon, l b 8.58 Viscosity at 25 C., cps4,0007,000

OH-lNA IN URETHANE COATINGS 5 When employed as the second componenttogether with NCO-1 1 or NCO-3 2 in a proportion'of NCO/OH: 1.2/1.0

OH-INA gives films which are hard, tough, and char 7 acterized byexcellent solvent resistance. They are, however, somewhat less hard andtough, and have a somewhat diminished solvent resistance, compared withthe films of Example 2, but are more flexible than the films of Example2. Chemical and water resistances are excellent. The films prepared atNCO/ OH=2.0/ 1.0 are harder, tougher and of a greater resistance thanthe films rat NCO/OH=1.2/ 1.0.

Example 2 (OH] .NB)

Reactants Mols Parts Weight, percent Polyoxypropylene derivative ofN,N,N',N- tetrakis(2-hydroxypropyl)ethylene diamine, M. 524 2 3, 144 68.8 Tolylene diisocyanate (80/20; 2,4/2,6) 1 522 11. 2 2-Ethoxyethylacetate 457 10 Xylene 457 10 NCO-1 is the NCO-terminated reactionproduct of three mols of TDI with one mol of T? 440 polyol (propyleneoxide agditizrioproduct of trimethylolpropane having a M.W. of a onNCO-3 is the NCO-terminated reaction product of two mols of NCO-1 withone mol of P 410 polyol (polypropylene glycol, M.W, about 410).

Numerous other organic polyisocyanates can be used as well as NCO-1 andNCO 3, such as, for example, trl TDI adduct of trimethylolpropane orhexanetriol, the phenylurethanes of any of the foregoing, TDI, MDI, andthe like.

Procedure.Same as in Example 1.

Properties of OH-1NB:

NCO/ OH 1/4 Average molecular weight 1224 Average equivalent weight 204Hydroxyl num ber 275 Percent hydroxyl 8.35 Properties of OH1NB solution:

Nonvolatile, percent 80 Weight per gallon, lb 8.7 Viscosity at 25 C.,cps 8,*000-10,000

OH-lNB IN URETHANE COATINGS When employed as the second componenttogether with NCO-l or NCO3 in proportion of NCO/OH=2.0/1.0, OH-lNBgives very hard and very solvent-resistant films. They are superior tothe films of Example 1 in respect of hardness and solvent resistance butare less flexible.

Example 3 (OH1NC) Reaetants Mols Parts TDI (80/20; 2,4/2,6) 1 174Polyoxypropylene derivative of N,N,N,N-tetrak1s(2- hydroxypropybethylenediamine (6 PO units), M.W. 640. 2 1, 280 2-Ethoxyethyl acetate 313Xylene 3113 Preparation of OH1NC.Same as in Example 1.

Properties of OH-lNC:

NCO/ OH 1/4 Average molecular Weight 1460 Average equivalent weight 245Hydroxyl number 228 Percent hydroxyl 6.9

OH-INC IN URETHANE SURFACE COATINGS When employed as the secondcomponent together with NCO-1 or NCO3 in the NCO/OH proportions ofExample 1, OH-lNC gives urethane films which are slightly less flexiblebut which have slightly greater solvent resist-ance than the films ofExample 1. Chemical resistance and water immersion resistance areexcellent.

Example 4 (OH1ND) Reactants Mols Parts TDI so 20; 2,4/2,6) 1 174Polyoxypropylene derivative of triisopropanohamine ('lIPA+3 mols ofpropylene oxide), (M.W. 368) 2 736 Z-Ethoxyethyl acetate 114 Xylene 141Preparation of OH-1ND.-Same as in Example 1. Properties of OH-lND:

NCO/OH 1/3 Average molecular weight 916 Average equivalent weight 229Hydroxyl number 1 245 Percent hydroxyl 7.4

OH1N'D IN URETHANE SURFACE COATINGS When employed as the secondcomponent together with NCO-1 or NCO-3 in the NCO/OH proportions of EX-ample 1, OH/ 1ND gives urethane films which are less flexible but whichhave greater solvent resistance than the films of Example 1. Chemicalresistance and water immersion resistance are excellent.

Example 5 I (0H-1NE) Reaetants Mols Parts Phenylene diisoeyanate 1 160Monoethylene oxide addition product or a polyoxypropylene derivative of'IIPA having a M.W. of 640. 2 1, 280 Z-Ethoxyethyl acetate 307 Xylene307 Preparation of OH1NE.-Same as in Example 1. Properties of OI-L-INE:

NCO/ OH 1/3 Average molecular weight 1444 Average equivalent Weight 361Hydroxyl number 155 Percent hydroxyl 4.7

.OH-lNE IN URETHANE SURFACE COATINGS When employed as the secondcomponent together with NCO-1 or NCO-3 in the NCO/ OH proportions ofExample 1, 0H-1NE gives urethane films which are more flexible but whichhave less solvent resistance than the films of Example 1. Chemicalresistance and water im- Percent hydroxyl 5.03

ioH lNF IN URETHAN-E SURFACE COATINGS When employed as the secondcomponent together with NCO-1 or NCO-3 in the NCO/OH proportions ofExample 1, OH-lNF gives urethane films which are more flexible but whichhave less solvent resistance than the films of Example 1. Chemicalresistance and Water immersion resistance are excellent.

Exizmple 7 (OH-1NG) Reactants Mols Parts 'IDI (/20; 2,4/2,6) 1 174Addition product of 8 mols of propylene oxide to one mol of N,N,N,N-tetrakis(Z-hydroxy-propyDethyI- ene diamine (M.W. 780) 2 1, 5602-Ethoxyethyl acetate 372 Xylene 372 Preparation of OH-1NG.Same as inExample 1. Properties of (DH-INF:

NCO/ OH 1/ 4 Average molecular weight 1740 Average equivalent Weight 290Hydroxyl number 194 Percent hydroxyl 5.86

OH-lNG IN UBETHANE SURFACE COATINGS When employed as the secondcomponent together with NCO-l or NCO3 in the NCO/ OH proportions of EX-ample 1, OH-ING gives urethane films which are very close in propertiesto those of Example 1. Chemical resistance and Water immersionresistance are excellent.

Example 8 (OH-1N H) Reactants Mols Parts TDI (2,1) 1 114 Additionproduct of 12 mols of propylene oxide to one mol of N ,N,N,N-tetrakis(2-hydroxy-propyl) ethylene diamine (M.W. 1,000) 2 2,0002-Ethoxyethyl acetate 466 Xylene 466 Preparation of OH-lNH..Same as inExample 1.

Properties of OH-lNH:

NCO/ OH l/4 Average molecular weight 2180 Average equivalent weight 363Hydroxyl number 159 P-ercent'hydroxyl 4.8

OH-INH IN URETHANE SURFACE COATINGS When employed as the secondcomponent together with NCO-1 or NCO-3 in the NCO/ OH proportions ofExample 1, OH-lNH gives urethane films which are more flexible but whichhave less solvent resistance than the films of Example 1. Chemicalresistance and Water immersion resistance are excellent.

Example 9 (OH-1ND Reactants Mols Parts TDI (80/20; 2,4/2,6) 1 174Addition product of 4 mols of propylene oxide and one mol of ethyleneoxide to one mol of TIPA (M.W.

496) 2 992 2-Ethoxyethy1 acetate 146 Xy n 146 Preparation of OHlNI.-Sameas in Example 1.

Properties of OH-1NIz NCO/OH 1/3 Average molecular weight 1172 Averageequivalent 293 Hydroxyl number 191 Percent hydroxyl 5.8

OH-lNI IN URETHANE SURFACE COATINGS When employed as the secondcomponent together with NCO-1 01' NCO3 in the NCO/ OH proportions ofExample 1, OH-lNI gives urethane films which are very close inproperties to those of Example 1. Chemical resistance and waterimmersion resistance are excellent.

Example 10 (OH-1N1) Reactants Mols Parts TDI (80/20; 2,4/2,6) 1 174N,N,N, -tetrakis(2 hydroxypropyl)ethylene diamine addition product withfour propylene oxide units and one ethylene oxide unit (M.W. 575) 2 1,150 Z-Ethoxyethyl ac 284 Xylene 234 Preparation of OH-1NJ.-Same as inExample 1.

Properties in OH-INI NCO/OH 1/4 Average molecular weight 1330 Averageequivalent weight 222 Hydroxyl number 252 Percent hydroxyl 7.6

{OH-1N3 IN URETHANE SURFACE COATINGS When employed as the secondcomponent together with NCO-l or NCO-3 in the NCO/ OH proportions ofExam 84 ple 1, OH-INI gives urethane films which are less flexible butwhich have greater solvent resistance than the films of Example 1.Chemical resistance and water immersion resistance are excellent.

Example 11 (OH-INK) Reactants Mols Parts TDI (/20; 2,4/2,6) 1 174Addition product of 9 mols of propylene oxide to one mol of TIPA (M.W.700) 2 1, 400 2-Ethoxyethyl acetate 197 Xylene 197 Preparation ofOHlNK.-Same as in Example 1..

Properties of OH-lNK:

NCO/OH 1/ 3 Average molecular Weight 1610 Average equivalent weight 402Hydroxyl number 139 Percent hydroxyl 4.2

OH1NK IN URETHANE SURFACE COATINGS When employed as the second componenttogether with .NCO-l or NCO-3 in the NCO/ OH proportions of Exams ple l,OH-1NK gives urethane films which are more flexible but which have lesssolvent resistance than the films of Example 1. Chemcial resistance andwater im- Procedure.2190 parts of the polyoxypropylene derivative oftriisopropanolamine, 361 parts of Z-ethoxyethyl acetate and 361 partsxylene are charged into a 5-liter reaction flask and are stirred gently.Tolylene diisocyanate is 'added gradually in portions. The temperatureof the strongly exothermic reaction is kept below 60 C.

After the exothermic reaction stops, the contents of the reaction flaskare heated at 70 C. for 3 hours. Thereafter, the contents are cooled andbottled.

Properties of OH-l32N:

NCO/OH 1/2.25 Average molecular weight 1440 Average equivalent weight288 Hydroxyl number Percent hydroxyl 5.9

Properties of OH-132N solutions:

Nonvolatile, percent 80 Weight per gallon, lb 8.72

Viscosity at 25 C., cps 10,000l2,000

DH-132N IN URETHANE COATINGS When employed as the second componenttogether with NCO-1 or NCO-3 in proportion of NCO/ OH=1.2/ 1.0,

OH-132N gives urethane films which are extremely hard,

tough, and characterized by a very high solvent resistance.

Chemical resistance and water resistance are excellent.

- It is to be understood that the invention is not limited to the exactdetails of operation or exact compounds shown and described, as obviousmodifications and equivalents will be apparent to one skilled in theart, and the invention is therefore to be limited only by the scope ofthe appended claims.

I claim:

1. A hydroxy-terminated urethane composition prepared by mixing andreacting together about one molar proportion of arylene diisocyanate (a)selected from the group consisting of phenylene diisocyanate, tolylenediisocyanate, and diphenylmethane-4,4-diisocyanate, with about two molarproportions of tertiary amine nitrogencontaining polyether polyol (b),said tertiary amine nitrogen-containing polyether polyol (b) beingselected from the group consisting of polyols having the formulas:

wherein Z is an alkylene radical containing from two through six carbonatoms, wherein n is a number from one to three, inclusive, and wherein xis a number from zero to one, inclusive, to produce the desiredhydroxyterminated urethane composition, the initial reaction temperaturebeing not greater than about sixty degrees centigrade.

2. A hydroxy-terminated urethane composition according to claim 1,wherein the arylene diisocyanate (a) is tolylene diisocyanate and thetertiary amine nitrogencontaining polyether polyol (b) is an alkyleneoxide addition product of triisopropanolamine having the formula:

wherein n is a number from one to three, inclusive, and wherein x is anumber from zero to one, inclusive.

3. A hydroxy-terminated urethane composition ac cording to claim 1wherein the arylene diisocyanate (a) is tolylene diisocyanate and thetertiary amine nitrogencontaining polyether polyol (b) is anN,N,N,N-tetrakis (Z-hydroxypropyDethylene diamine-alkylene oxideaddition product having the formula:

wherein Z is an alkylene radical containing from two through six carbonatoms, wherein n is a number from one to three, inclusive, and wherein xis a number from zero to one, inclusive.

4. A hydroxy-terminated urethane composition according to claim 1wherein the average equivalent weight is between about 200 and about400.

5. A solution of a hydroxy-terminated urethane composition according toclaim 1 in a surface coating solvent which is nonreactive therewith.

6. A urethane coating composition including as one component ahydroxy-terminated urethane according to claim 1 and including anorganic polyisocyanate as a second component.

7. A coating composition according to claim 6, including an organicsurface coating solvent which is nonreactive with both the components ofthe coating composition and the polyurethane product of their reaction.

8. A process for the production of a hydroxy-terminated urethanecomposition which comprises mixing and reacting together about one molarproportion of arylene to diisocyanate (a) selected from the groupconsisting of 'phenylene diisocyanate, tolylene diisocyanate, anddiphenylmethane-4,4'-diisocyanate, with about two molar proportions oftertiary amine nitrogen-containing polyether polyol (b), said tertiaryamine nitrogen-containing polyether polyol (b) being selected from thegroup consisting of polyols having the formulas: a

r r H(OC3HB) nOCH-CH2 CHFCHO(C3HBO)11H (1H3 /NZN (1H '-'(0 CEHQ) x(003256) CH-CHQ GET-CHO (GaHaO) H and (IE3 (6H3 CHa-CHO (oaHoo) 11HH-(OCzH4) 1(0 C n0 CHCH2N CH CHr-CHO (CaHeO) DH wherein Z is an alkyleneradical containing from two through six carbon atoms, wherein n is anumber from one .to three, inclusive, and wherein x is a number fromzero to one, inclusive, to produce the desired hydroxyterminatedurethane composition, the initial reaction temperature being not greaterthan about sixty degrees centigrade.

9. A process for producing a hydroxy-itenninated urethane compositionaccording to claim 8, wherein the arylene diisocyanate (a) is tolylenediisocyanate and the tertiary amine nitrogen-containing polyether polyol(b) is an alkylene oxide addition product of triisopropanolamine havingthe formula:

wherein n is a number from one to three, inclusive, and wherein x is anumber from zero to one, inclusive.

10. A process for producing a hydroxyaterminated urethane compositionaccording to claim 8, wherein the arylene diisocyanate (a) is tolylenediisocyanate and the tertiary amine nitrogen-containing polyether polyol(b) is an N,N,N, '-tetrakis(2-hydroxypropyl)ethylene diamine-alkyleneoxide addition product having the formula:

wherein Z is an alkylene radical containing from two through six carbonatoms, wherein n is a number from one to three, inclusive, and wherein xis a number from zero to one, inclusive.

11. A hydroxy-terminaited urethane composition prepared by mixing andreacting about one molar proportion of arylene diisocyanate (a) selectedfrom the group consisting of phenylene diisocyanate, tolylenediisocyanate, and diphenylmethane-4,4'-diisocyanate, with about twomolar proportions of tertiary amine nitrogen-containing polyether polyol(b), said tertiary amine nitrogen-containing polyether (b) beingselected from the group consisting of polyols having the formulas:

and 1 1 on, CH3 GHQ-(3H0 (C3350) nH H(O c111, x 0 03130.10 JH-CIn-N on,

Ulla-( 3H0 (031E160) 11H wherein Z is an alkylene radical containingfrom two through six carbon atoms, wherein n is a number from one tothree, inclusive, and wherein x is a number from zero to one, inclusive.

12. A process for the production of a hydroxy-ter minated urethanecomposition, which consists in mixing and reacting about one molarproportion of arylene disisocyanate (a) selected from the groupconsisting of phenylene diisocyanate, tolylene diisocyanate, anddiphenylmethane-4,4-diisocyanate, with about two molar proportions oftertiary amine nitrogen-containing polyether polyol (b), said tertiaryamine nitrogen-containing polyether polyol (b) being selected from thegroup consisting of polyols having the formulas:

CH3 CH3 H(OC3Hfl)nO ('JH-GH: CHPICHO (CQHBO) nH CH3 N-Z-N CH3 H(O 0,114)(003116) .10 (in-oh: onhbno oarrfionn and CH3 CH3 Clix-( 3H0 (CgHeO) HH(OOzH4)x(OC;Hs) nO( JH-CHzN CH3 1 CHzCHO (CaH O) H wherein Z is analkylene radical containing from two through six carbon atoms, wherein nis a number from one to three, inclusive, and wherein x is a number fromzero to one, inclusive.

References Cited in the file of this patent UNITED STATES PATENTS2,814,605 Stilmar Nov. 26, 1957 2,858,298 Burt Oct. 28, 1958 r 2,866,774Price Dec. 30, 1958 2,871,226 McShane Jan. 27, 1959 2,927,905 Eckert'Mar. 8, 1960 2,948,691 Windemuth et a1. Aug. 9, 1960 2,959,618 KyridesNov. 8, 1960 2,962,524 Hostettler Nov. 29, 1960 FOREIGN PATENTS 206,295Australia Feb. 10, 1955 205,456 Australia Jan. 4,

OTHER REFERENCES Abernathy: Rubber World, March 1955, pages 765- 769.

Ogden: Rubber World, July 1957, pages 537-542.

Chemical and Engineering News, Jan. 2, 1957, page 78.

E. -I. du Pont de Nemours and 00., Wilmington, Del., ContinuousPreparation of Urethane Foam Prepolymer, HR-29, July 1958.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,105,063 September 24, 1963 Adolfas Damusis It is hereby certified thaterror appears in the above numbered patent requiring correction and thatthe said Letters Patent should read as corrected below.

Column 3, line '73, for "0.2%" read 0.02% column 4, line 17, for"2-ethoxylethyl" read 2-ethoxyethyl column 5, in the table for "Example4, first column, line 2 thereof, for "triisopropanol,amine" readtriisopropanolamine same table, second column, line 4 thereof, for "141"read 114 same column 5, line 72, for "OH/1ND" read 0H1ND column 6, line39, for "NH-INF" read OH-lNF line 65, for "OH-1NF" read OH-lNG column 8,line 29, for "Chemcial" read Chemical line 60, for "solutions" readsolution Signed and sealed this 9th day of June 1964.

(SEAL) Attest:

ERNEST W SWIDER EDWARD J. BRENNER Attesting Officer Commissioner ofPatents

1. A HYDROXY-TERMINATED URETHANE COMPOSITION PREPARED BY MIXING ANDREACTING TOGETHER ABOUT ONE MOLAR PROPORTION OF ARYLENE DIISOCYANATE (A)SELECTED FROM THE GROUP CONSISTING OF PHENYLENE DIISOCYANATE, TOLYLENEDIISOCYANATE, AND DIPHENYLMETHANE-4,4''-DISOOCYANATE, WITH ABOUT TWOMOLAR PROPORTIONS OF TRTIARY AMINE NITROGENCONTAINING POLYETHER POLYOL(B), SAID TERTIARY AMINE NITROGEN-CONTAINING POLYETHER POLYOL (B) BEINGSELECTED FROM THE GROUP CONSISTING OF POLYOLS HAVING THE FORMULAS: